Free radical addition to olefins. Part 20.-A reinvestigation of the addition of methyl radicals to fluoroethylenes.

The addition of methyl radicals to fluoroethylenes has been reinvestigated using both azomethane and di-t-butylperoxide as initiators. As in the previous work, excess methyl iodide was added to promote a chain reaction. Unlike the previous study, telomeric products of low volatility were identified and quantitatively estimated. Correction of the monomeric product ratios by addition of the appropriate telomers had a significant effect on the relative Arrhenius parameters in some cases. New values of the activation parameters for the addition of methyl radicals to vinyl fluoride, 1, 1-difluoroethylene, trifluoroethylene and tetrafluoroethylene relative to ethylene, are presented.